CN108530311A - A kind of preparation method of amido alkyl naphthols - Google Patents
A kind of preparation method of amido alkyl naphthols Download PDFInfo
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- CN108530311A CN108530311A CN201810272493.2A CN201810272493A CN108530311A CN 108530311 A CN108530311 A CN 108530311A CN 201810272493 A CN201810272493 A CN 201810272493A CN 108530311 A CN108530311 A CN 108530311A
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- molar ratio
- betanaphthol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/08—Preparation of carboxylic acid amides from amides by reaction at nitrogen atoms of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
- C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
Abstract
The present invention relates to a kind of preparation methods of amido alkyl naphthols, this method refers to that Beta Naphthol 99MIN, amide, aldehyde compound and catalyst antimony halides are added in reactor successively, it is reacted under 50 ~ 80 DEG C of condition of water bath heating, reaction mixture is obtained after the reaction was complete；Crude product is obtained after the reaction mixture is washed, the crude product is again to get pore amide base alkyl naphthol after absolute ethyl alcohol recrystallization separation.The present invention is simple, production cost is low efficient, and product yield may be up to 98.3%, have preferable prospects for commercial application.
Description
Technical field
The present invention relates to synthetic organic chemical art more particularly to a kind of preparation methods of amido alkyl naphthols.
Background technology
Amido alkyl naphthols, as a kind of important organic synthesis intermediate, because of special bioactivity and pharmacology
Characteristic has important use in the synthesis of medicine, pesticide, asymmetric syntheses and natural products.Especially by amido alkyl
The derivative for the amido alkyl naphthols that naphthols is transformed has it significant in terms for the treatment of hypertension and angiocardiopathy
Effect, and its derivative is formed by ligand and is also widely used as catalyst
Reza Shaterian in 2008 etc. are reported with FeCl3•SiO2For heterogeneous catalysis, betanaphthol, aldehyde and acetonitrile or
Acetamide occurs class Ritter and corresponding 1- acetylaminos alkyl beta naphthal is obtained by the reaction, and used catalyst is cheap and easy to get, can return
It receives and utilizes；But when using acetonitrile as reactant, although this method mild condition, yield are higher（65~88%）, but the reaction time is too long,
Longest needs 1200min, and wherein acetonitrile is both reactant and reaction dissolvent, and dosage is more；When using acetamide as reactant,
Although this method reaction time is short（7~40min）, high income（77~94%）, but reaction temperature is higher（120℃）（Tetrahedron bulletin
（Tetrahedron Letters）, 2008,49,1297-1300）.
2012, Zhu etc. reported three（Triphenylphosphine）Ruthenous chloride is catalyzed three components of aromatic aldehyde, betanaphthol and amide
Reaction, higher yields obtain corresponding amido alkyl naphthols.Although this reaction used catalyst asepsis environment-protecting, this reaction is not
Only need nitrogen protection, it is also necessary to which toluene makees solvent, and the reaction time is long（600~720min）（Chemical Society of South Korea is notified to
（Bull. Korean Chem. Soc. 2012, 33（8）2799-2802）.The researchs such as Tamaddon in 2011 find ZnCl2/
SiO2Betanaphthol, aldehyde and benzene acetonitrile can also be effectively catalyzed, three groups of classification Ritter reactions occur, obtain corresponding amido alkyl
Base naphthol compound, but this reaction yield is relatively low（70%）, temperature is higher（100℃）（Journal of Molecular Catalysis A:Chemistry（Journal of
Molecular Catalysis A: Chemical）2011,337,52-55）.
Antimony category nitrogen group element（15 races）, it is a kind of silvery grey metal of band.The two class halogenations that antimony is formed
Object --- SbX3And SbX5, it is common lewis acid.Wherein trihalid（SbF3、SbCl3、SbBr3And SbI3）Usually tie
Crystalline substance, the easy moisture absorption are acid weaker；Pentahalide（SbF5And SbCl5）It is very strong lewis acid for liquid.Antimony halides is as catalysis
It is easy to get, activity height, and is post-processed simply when agent, is widely used in organic synthesis in recent years.2012, the reports such as Moeinpour
SbCl3-SiO2It is catalyzed one pot of three component reaction of betanaphthol, aldehyde and acetamide, high yield obtains corresponding product 1- acetamidos
Alkyl-beta naphthal compound.Although this reaction is efficient, the time is short, and reaction temperature is higher（120℃）, oil bath heating is needed,
Simultaneous reactions post-processing is more complex, needs that ethyl acetate lysate, separating liquiding catalyst is first used then to be concentrated to give crude product, most
Recrystallize to obtain target product (synthesis inorganic, metal is organic and nano metal is chemical and reactivity again afterwards（Synthesis and
Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 2012,42,
278–281）.And the reaction that antimony halides is directly prepared to amido alkyl naphthols for three component one kettle ways at present yet there are no document
Report.
Although being recorded from document as can be seen that above method reaction condition is mild, yield is higher, and there are still many to ask
Topic：(1) the reaction time is long；(2) reaction temperature is high；(3) need reaction dissolvent, reaction cost high；(4) post-reaction treatment is complicated.Therefore
A kind of method of efficient, quick, resource-effective synthesizing amide base alkyl naphthol is developed all the time by the very big pass of people
Note.
Invention content
Technical problem to be solved by the invention is to provide a kind of inexpensive, efficient, quick amido alkyl naphthols
Preparation method.
To solve the above problems, a kind of preparation method of amido alkyl naphthols of the present invention, it is characterised in that：It should
Method refers to that betanaphthol, amide, aldehyde compound and catalyst antimony halides are added in reactor successively, in 50 ~ 80 DEG C of water-baths
It is reacted under heating condition, reaction mixture is obtained after the reaction was complete；Crude product is obtained after the reaction mixture is washed, this is thick
Product is again to get pore amide base alkyl naphthol after absolute ethyl alcohol recrystallization separation；The betanaphthol and the antimony halides
Molar ratio is 1：0.10~1：0.30；The molar ratio of the betanaphthol and the amide is 1：0.9~1：1.2；The betanaphthol with
The molar ratio of the aldehyde compound is 1：1.0~1：1.3.
The antimony halides refers to SbF3、SbCl3、SbBr3、SbI3、SbF5And SbCl5In any one.
The structural formula of the aldehyde compound is R1CHO；Wherein R1For aryl, five yuan of aromatic heterocyclics, contain 2 ~ 7 carbon atoms
Alkyl in any one.
The structural formula of the amide is R2CONH2；Wherein R2One in alkyl or amino for aryl, containing 2 ~ 4 carbon atoms
Kind.
The washing refers to being washed using absolute ethyl alcohol.
Compared with the prior art, the present invention has the following advantages：
1, since the reaction of the present invention is carried out at 50 ~ 80 DEG C, heating water bath, therefore reaction condition is mild, it is easy to operate.
2, since the present invention is using the good catalyst of activity, catalyst charge is no more than 30%, is once added all anti-
Material is answered, to foreshorten in the reaction time within 90 minutes, because the method is simple, efficiently, product yield is up to 98.3%.
3, since raw material of the present invention is easy to get, any co-catalyst and solvent are not required to, therefore reduce production cost, have compared with
Good prospects for commercial application.
Specific implementation mode
A kind of preparation method of 1 amido alkyl naphthols of embodiment, this method refer to successively by betanaphthol, amide, aldehydes
Compound and catalyst antimony halides are added in reactor, are reacted under 55 DEG C of condition of water bath heating, and entire reaction process is used
Thin layer chromatography tracks, i.e., sampled every 3 ~ 5 minutes, be respectively dropped on silica gel plate with capillary（It is dissolved with ethyl acetate）Instead
It answers liquid spotting, material liquid benzaldehyde point sample, at two point samples on the same line, then silica gel plate is put into and fills volume ratio
（mL/ mL）It is 1：In the exhibition bottle of 4 ethyl acetate and the mixed liquor of petroleum ether.After the completion of limp, then silica gel plate is placed on ultraviolet
It is observed under lamp or in iodine flask, if the point not flushed with material liquid benzaldehyde in reaction solution, shows that the reaction was complete, at this time
Reaction mixture.
Reaction mixture after absolute ethyl alcohol washs crude product, the crude product again through absolute ethyl alcohol recrystallization separation after,
Up to pore amide base alkyl naphthol.
After tested, reaction time 50min, yield 98.3%.
Wherein：Betanaphthol and SbCl3Molar ratio be 1：0.15；The molar ratio of betanaphthol and acetamide is 1：1.0；β-naphthalene
The molar ratio of phenol and benzaldehyde is 1：1.1.
The preparation method is the same as that of Example 1 for a kind of 2 amido alkyl naphthols of embodiment, and reaction temperature is 50 DEG C.
After tested, reaction time 65min, yield 90.6%.
Wherein：Betanaphthol and SbCl3Molar ratio be 1：0.20；The molar ratio of betanaphthol and propionamide is 1：0.9；β-naphthalene
The molar ratio of phenol and 4- tolyl aldehydes is 1：1.2.
The preparation method is the same as that of Example 1 for a kind of 3 amido alkyl naphthols of embodiment, and reaction temperature is 65 DEG C.
After tested, reaction time 70min, yield 87.8%.
Wherein：Betanaphthol and SbF3Molar ratio be 1：0.10；The molar ratio of betanaphthol and benzamide is 1：1.1；β-
The molar ratio of naphthols and 4- chlorobenzaldehydes is 1：1.2.
The preparation method is the same as that of Example 1 for a kind of 4 amido alkyl naphthols of embodiment, and reaction temperature is 80 DEG C.
After tested, reaction time 65min, yield 91.5%.
Wherein：Betanaphthol and SbBr3Molar ratio be 1：0.25；The molar ratio of betanaphthol and benzamide is 1：1.0；β-
The molar ratio of naphthols and 2- tolyl aldehydes is 1：1.2.
The preparation method is the same as that of Example 1 for a kind of 5 amido alkyl naphthols of embodiment, and reaction temperature is 70 DEG C.
After tested, reaction time 90min, yield 70.2%.
Wherein：Betanaphthol and SbCl5Molar ratio be 1：0.15；The molar ratio of betanaphthol and acetamide is 1：1.1；β-naphthalene
The molar ratio of phenol and n-Heptaldehyde is 1：1.3.
The preparation method is the same as that of Example 1 for a kind of 6 amido alkyl naphthols of embodiment, and reaction temperature is 75 DEG C.
After tested, reaction time 55min, yield 88.6%.
Wherein：Betanaphthol and SbF5Molar ratio be 1：0.10；The molar ratio of betanaphthol and urea is 1：1.2；Betanaphthol
Molar ratio with 2,4- dichlorobenzaldehydes is 1：1.1.
The preparation method is the same as that of Example 1 for a kind of 7 amido alkyl naphthols of embodiment, and reaction temperature is 65 DEG C.
After tested, reaction time 86min, yield 92.1%.
Wherein：Betanaphthol and SbI3Molar ratio be 1：0.30；The molar ratio of betanaphthol and acetamide is 1：1.2；β-naphthalene
The molar ratio of phenol and 4- cyanobenzaldehydes is 1：1.0.
The preparation method is the same as that of Example 1 for a kind of 8 amido alkyl naphthols of embodiment, and reaction temperature is 55 DEG C.
After tested, reaction time 74min, yield 89.7%.
Wherein：Betanaphthol and SbCl3Molar ratio be 1：0.25；The molar ratio of betanaphthol and propionamide is 1：1.1；β-naphthalene
The molar ratio of phenol and 4- bromobenzaldehydes is 1：1.2.
The preparation method is the same as that of Example 1 for a kind of 9 amido alkyl naphthols of embodiment, and reaction temperature is 70 DEG C.
After tested, reaction time 82min, yield 91.7%.
Wherein：Betanaphthol and SbCl5Molar ratio be 1：0.15；The molar ratio of betanaphthol and benzamide is 1：1.2；β-
The molar ratio of naphthols and 4- benzonitrile formaldehyde is 1：1.0.
The preparation method is the same as that of Example 1 for a kind of 10 amido alkyl naphthols of embodiment, and reaction temperature is 60 DEG C.
After tested, reaction time 84min, yield 87.3%.
Wherein：Betanaphthol and SbBr3Molar ratio be 1：0.20；The molar ratio of betanaphthol and acetamide is 1：1.1；β-naphthalene
The molar ratio of phenol and 4- nitrobenzaldehydes is 1：1.0.
The preparation method is the same as that of Example 1 for a kind of 11 amido alkyl naphthols of embodiment, and reaction temperature is 75 DEG C.
After tested, reaction time 85min, yield 62.7%.
Wherein：Betanaphthol and SbF3Molar ratio be 1：0.15；The molar ratio of betanaphthol and benzamide is 1：1.2；β-
The molar ratio of naphthols and n-butanal is 1：1.3.
The preparation method is the same as that of Example 1 for a kind of 12 amido alkyl naphthols of embodiment, and reaction temperature is 65 DEG C.
After tested, reaction time 63min, yield, 86.3%.
Wherein：Betanaphthol and SbF5Molar ratio be 1：0.10；The molar ratio of betanaphthol and propionamide is 1：1.1；β-naphthalene
The molar ratio of phenol and 2- bromobenzaldehydes is 1：1.2.
The preparation method is the same as that of Example 1 for a kind of 13 amido alkyl naphthols of embodiment, and reaction temperature is 80 DEG C.
After tested, reaction time 83min, yield 72.4%.
Wherein：Betanaphthol and SbCl5Molar ratio be 1：0.30；The molar ratio of betanaphthol and urea is 1：1.2；Betanaphthol
Molar ratio with 2 furan carboxyaldehyde is 1：1.1.
The preparation method is the same as that of Example 1 for a kind of 14 amido alkyl naphthols of embodiment, and reaction temperature is 70 DEG C.
After tested, reaction time 75min, yield 90.3%.
Wherein：Betanaphthol and SbCl3Molar ratio be 1：0.25；The molar ratio of betanaphthol and urea is 1：1.2；Betanaphthol
Molar ratio with 4-methoxybenzaldehyde is 1：1.2.
Claims (5)
1. a kind of preparation method of amido alkyl naphthols, it is characterised in that：This method refers to successively by betanaphthol, amide, aldehyde
Class compound and catalyst antimony halides are added in reactor, are reacted under 50 ~ 80 DEG C of condition of water bath heating, after the reaction was complete
Obtain reaction mixture；After the reaction mixture is washed crude product, the crude product again through absolute ethyl alcohol recrystallization separation after,
Up to pore amide base alkyl naphthol；The molar ratio of the betanaphthol and the antimony halides is 1：0.10~1：0.30；β-the naphthalene
The molar ratio of phenol and the amide is 1：0.9~1：1.2；The molar ratio of the betanaphthol and the aldehyde compound is 1：1.0~
1：1.3.
2. a kind of preparation method of amido alkyl naphthols as described in claim 1, it is characterised in that：The antimony halides refers to
SbF3、SbCl3、SbBr3、SbI3、SbF5And SbCl5In any one.
3. a kind of preparation method of amido alkyl naphthols as described in claim 1, it is characterised in that：The aldehyde compound
Structural formula be R1CHO；Wherein R1For any one in aryl, five yuan of aromatic heterocyclics, the alkyl containing 2 ~ 7 carbon atoms.
4. a kind of preparation method of amido alkyl naphthols as described in claim 1, it is characterised in that：The structure of the amide
Formula is R2CONH2；Wherein R2One kind in alkyl or amino for aryl, containing 2 ~ 4 carbon atoms.
5. a kind of preparation method of amido alkyl naphthols as described in claim 1, it is characterised in that：The washing refers to adopting
It is washed with absolute ethyl alcohol.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061151A (en) * | 2004-10-15 | 2007-10-24 | 建筑研究和科技有限公司 | Polycondensation product based on aromatic or heteroaromatic compounds, method for the production thereof, and use thereof |
| CN105669484A (en) * | 2016-03-10 | 2016-06-15 | 陇东学院 | Preparation method of acylamino alkyl naphthol |
-
2018
- 2018-03-29 CN CN201810272493.2A patent/CN108530311A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061151A (en) * | 2004-10-15 | 2007-10-24 | 建筑研究和科技有限公司 | Polycondensation product based on aromatic or heteroaromatic compounds, method for the production thereof, and use thereof |
| CN105669484A (en) * | 2016-03-10 | 2016-06-15 | 陇东学院 | Preparation method of acylamino alkyl naphthol |
Non-Patent Citations (1)
| Title |
|---|
| FARID MOEINPOUR，等: "SbCl3-SiO2 Catalyzed Simple and Efficient One-Pot Synthesis of 1-Amidoalkyl-2-Naphthols Under Solvent-Free Conditions", 《SYNTHESIS AND REACTIVITY IN INORGANIC，METAL-ORGANIC，AND NANO-METAL CHEMISTRY》 * |
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